A water droplet size distribution dependent modeling of hydrate formation in water/oil emulsion

Experimental data on chord length distributions and growth rate during methane hydrate formation in water‐in‐oil emulsions were obtained in a high pressure stirring reactor using focused beam reflectance measurement and particle video microscope. The experiments were carried out at 274.2 K for 10–30% water cuts and agitation rates ranging from 200 to 500 rpm initially at 7.72 MPa. Rapid growth was accompanied by gradually decrease in rate. Free water was observed to become depleted during rapid growth while some water remained encapsulated inside hydrate layers constituting a mass transfer barrier. The apparent kinetic constants of methane hydrate formation and free‐water fractions were determined using a newly developed kinetic model independent of the dissolution rate at the gas–oil interface. It was illustrated that continued growth depends on distribution and transfer of water in oil‐dominated systems. This perception accords with observations of hydrate film growth on suspended water droplet in oil and clarifies transfer limits in kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1010–1023, 2017     

Impact of water film thickness on kinetic rate of mixed hydrate formation during injection of CO2 into CH4 hydrate

In this work, nonequilibrium thermodynamics and phase field theory (PFT) has been applied to study the kinetics of phase transitions associated with CO₂ injection into systems containing CH₄ hydrate, free CH₄ gas, and varying amounts of liquid water. The CH₄ hydrate was converted into either pure CO₂ or mixed CO₂?CH₄ hydrate to investigate the impact of two primary mechanisms governing the relevant phase transitions: solid‐state mass transport through hydrate and heat transfer away from the newly formed CO₂ hydrate. Experimentally proven dependence of kinetic conversion rate on the amount of available free pore water was investigated and successfully reproduced in our model systems. It was found that rate of conversion was directly proportional to the amount of liquid water initially surrounding the hydrate. When all of the liquid has been converted into either CO₂ or mixed CO₂?CH₄ hydrate, a much slower solid‐state mass transport becomes the dominant mechanism. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3944–3957, 2015     

Nucleation curves of model natural gas hydrates on a quasi‐free water droplet

Heterogeneous nucleation probability distributions of gas hydrates on a water droplet that was supported by inert and immiscible perfluorocarbon oil, perfluorodecalin is studied. The guest gas used was a mixture of 90 mol % methane and 10 mol % propane. The probability distribution was measured using a high pressure automated lag time apparatus under the guest gas pressure range of 6.7–12.5 MPa and the cooling rate range of 0.002–0.02 K/s. Nucleation curves were derived for unit area of water surface. The nucleation rate per unit area of water surface that was contained in a glass sample cell, which differed significantly from that on a quasi‐free water droplet, is also derived. It is concluded that the nucleation curves in the presence of a solid wall should be normalized to the unit length of the three‐phase line at which water, guest gas, and the solid wall meet. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2611–2617, 2015     

Impact of the fluid flow conditions on the formation rate of carbon dioxide hydrates in a semi‐batch stirred tank reactor

CO₂ hydrate formation experiments are performed in a 20 L semi‐batch stirred tank reactor using three different impellers (a down‐pumping pitched blade turbine, a Maxblend?, and a Dispersimax?) at various rotational speeds to examine the impact of the flow conditions on the CO₂ hydrate formation rate. An original mathematical model of the CO₂ hydrate formation process that assigns a resistance to each of its constitutive steps is established. For each experimental condition, the formation rate is measured and the rate‐limiting step is determined on the basis of the respective values of the resistances. The efficiencies of the three considered impellers are compared and, for each impeller, the influence of the rotational speed on the rate‐limiting step is discussed. For instance, it is shown that a formation rate limitation due to heat transfer can occur at the relatively small scale used to perform our experiments. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4387–4401, 2015     

One‐dimensional productivity assessment for on‐field methane hydrate production using CO2/N2 mixture gas

The direct recovery of methane from gas hydrate‐bearing sediments is demonstrated, where a gaseous mixture of CO₂ + N₂ is used to trigger a replacement reaction in complex phase surroundings. A one‐dimensional high‐pressure reactor (8 m) was designed to test the actual aspects of the replacement reaction occurring in natural gas hydrate (NGH) reservoir conditions. NGH can be converted into CO₂ hydrate by a “replacement mechanism,” which serves double duty as a means of both sustainable energy source extraction and greenhouse gas sequestration. The replacement efficiency controlling totally recovered CH₄ amount is inversely proportional to CO₂ + N₂ injection rate which directly affecting solid ‐ gas contact time. Qualitative/quantitative analysis on compositional profiles at each port reveals that the length more than 5.6 m is required to show noticeable recovery rate for NGH production. These outcomes are expected to establish the optimized key process variables for near future field production tests. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1004–1014, 2015     

Induction time,storage capacity,and rate of methane hydrate formation in the presence of SDS and silver nanoparticles

In this communication, the kinetic parameters of methane hydrate formation (induction time, quantity and rate of gas uptake, storage capacity (SC), and apparent rate constant) in the presence of sodium dodecyl sulfate (SDS), synthetized silver nanoparticles (SNPs), and mixture of SDS?+?SNPs have been studied. Experimental measurements were performed at temperature of 273.65?K and initial pressure of 7?MPa in a 460?cm³ stirred batch reactor. Our results show that adding SDS, SNPs and their mixture increases the quantity of gas uptake, water to hydrate conversion, and SC of methane hydrate formation, noticeably. Using 300?ppm SDS increases the SC and the quantity of methane uptake 615, and 770%, respectively, compared with pure water. Investigating the hydrate growth rate at the start of hydrate formation process shows that, using SNPs, SDS, and their mixture increases the initial apparent rate constant of hydrate rate, considerably. Our results show that the system of methane?+?water?+?SDS 500?ppm?+?SNPs 45?µM represents the maximum value of initial apparent rate constant, compared with other tested systems.     

A crossover‐UNIQUAC model for critical and noncritical LLE calculations

A new model, named the crossover‐UNIQUAC model, has been proposed based on the crossover procedure for predicting constant‐pressure liquid–liquid equilibria (LLE). In this manner, critical fluctuations were incorporated into the classical UNIQUAC equation. Coexistence curves were estimated for systems having a diverse range of asymmetries. These systems included the LLE of five different mixtures, composed of nitrobenzene with one of the members of the alkane homologous family (either pentane, octane, decane, dodecane, or tetradecane), as well as an extra system having a different chemical nature, namely the mixture of n‐perfluorohexane and hexane, to further check the validity of the proposed approach. Using these nonideal mixtures, the validity of the new model was investigated within wide ranges, covering near‐critical to regions falling far away from the critical point. The graphical trends, as well as the quantitative comparison with experimental data indicated the good agreement of the proposed model results with the experimental data. A maximum AARD% value of 3.97% was obtained in calculating molar compositions by the proposed model for such challenging systems covering noncritical, as well as critical regions. In addition, to show the strength of the proposed crossover approach to describe properties other than LLE, molar heat capacities were investigated for the system of nitrobenzene + dodecane. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3094–3103, 2015     

Measurements of methane hydrate heat of dissociation using high pressure differential scanning calorimetry

The methane hydrate heat of decomposition was directly measured up to 20 MPa and 292 K using a high pressure differential scanning calorimeter (DSC). The methane hydrate sample was formed ex-situ using granular ice particles and subsequently transferred into the DSC cell under liquid nitrogen. The ice and water impurities in the hydrate sample were reduced by converting any dissociated hydrate into methane hydrate inside the DSC cell before performing the thermal properties measurements. The methane hydrate sample was dissociated by raising the temperature (0.5-1.0 K/min) above the hydrate equilibrium temperature at a constant pressure. The measured methane hydrate heat of dissociation (H→W+G), ΔH_d, remained constant at 54.44±1.45 kJ/mol gas (504.07±13.48 J/gm water or 438.54± 13.78 J/gm hydrate) for pressures up to 20 MPa. The measured ΔH_d is in agreement with the Clapeyron equation predictions at high pressures; however, the Clausius-Clapeyron equation predictions do not agree with the heat of dissociation data at high pressures. In conclusion, it is recommended that the Clapeyron equation should be used for hydrate heat of dissociation estimations at high pressures.     

Determination of the activation energy and intrinsic rate constant of methane gas hydrate decomposition

Experimental data on the kinetics of methane gas hydrate decomposition are reported. The isothermal/isobaric semi‐batch stirred‐tank reactor, used by Kim et al. (1987), was modified to include an on‐line particle size analyzer. The experiments were conducted at temperatures ranging from 274.65 K to 281.15 K and at pressures between 3.1 and 6.1 MPa. The model of Clarke and Bishnoi (1999, 2000) was used to determine the intrinsic rate constant. It was found that the activation energy for methane hydrate decomposition is 81 kJ/mol and the intrinsic rate constant of decomposition is 3.6 × 10⁴ mol/m² Pa.s.     

An investigation on gas hydrate formation and slurry viscosity in the presence of wax crystals

Clarifying the interaction effect between hydrate and wax is of great significance to guarantee operation safety in deep water petroleum fields. Experiments in a high‐pressure hydrate slurry rheological measurement system were carried out to investigate hydrate formation and slurry viscosity in the presence of wax crystals. Results indicate that the presence of wax crystals can prolong hydrate nucleation induction time, and its influence on hydrate growth depends on multiple factors. Higher stirring rate can obviously promote hydrate growth rate, while its influence on hydrate nucleation induction time is complicated. Higher initial pressure will promote hydrate formation. Gas hydrate slurry shows a shear‐thinning behavior, and slurry viscosity increases with the increase of wax content and initial pressure. A semiempirical viscosity model showing a well‐fitting is established for hydrate slurry with wax crystals by considering the aggregation and breakage of hydrate particles, wax crystals, and water droplets. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3502–3518, 2018     

0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响

The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate(methane-SDS hydrates),were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior.The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing.The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring;the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure;the compaction of hydrate after its formation lowered its stability,i.e.,increased its dissociation rate.The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down,or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure.It was found that the dissociation rate of methane hydrate varied with the temperature(ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter.The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.     

Study of the Kinetics and Morphology of Gas Hydrate Formation

The kinetics and morphology of ethane hydrate formation were studied in a batch type reactor at a temperature of ca. 270–280 K, over a pressure range of 8.83–16.67 bar. The results of the experiments revealed that the formation kinetics were dependant on pressure, temperature, degree of supercooling, and stirring rate. Regardless of the saturation state, the primary nucleation always took place in the bulk of the water and the phase transition was always initiated at the surface of the vortex (gas‐water interface). The rate of hydrate formation was observed to increase with an increase in pressure. The effect of stirring rate on nucleation and growth was emphasized in great detail. The experiments were performed at various stirring rates of 110–190 rpm. Higher rates of formation of gas hydrate were recorded at faster stirring rates. The appearance of nuclei and their subsequent growth at the interface, for different stirring rates, was explained by the proposed conceptual model of mass transfer resistances. The patterns of gas consumption rates, with changing rpm, have been visualized as due to a critical level of gas molecules in the immediate vicinity of the growing hydrate particle. Nucleation and decomposition gave a cyclic hysteresis‐like phenomena. It was also observed that a change in pressure had a much greater effect on the rate of decomposition than it did on the formation rate. Morphological studies revealed that the ethane hydrate resembles thread or is cotton‐like in appearance. The rate of gas consumption during nucleation, with different rpm and pressures, and the percentage decomposition at different pressures, were explained precisely for ethane hydrate.     

Analysis of solar‐driven gasification of biochar trickling through an interconnected porous structure

The efficient transfer of high‐temperature solar heat to the reaction site is crucial for the yield and selectivity of the solar‐driven gasification of biomass. The performance of a gas‐solid trickle‐bed reactor constructed from a high thermal conductivity porous ceramic packing has been investigated. Beech char particles were used as the model feedstock. A two‐dimensional finite‐volume model coupling chemical reaction with conduction, convection, and radiation of heat within the packing was developed and tested against measured temperatures and gasification rates. The sensitivity of the gasification rate and reactor temperatures to variations of the packing's pore diameter, porosity, thermal conductivity, and particle loading was numerically studied. A numerical comparison with a moving bed projected a more uniform temperature distribution and higher gasification rates due to the increased heat transfer via combined radiation and conduction through the trickle bed. © 2014 American Institute of Chemical Engineers AIChE J, 61: 867–879, 2015     

Probability distributions of gas hydrate formation

Induction time distributions for gas hydrate formation were measured for gas mixtures of methane + propane at pressures up to 11.3 MPa using a high‐pressure automated lag time apparatus (HP‐ALTA). Measurements were made at subcooling temperatures between 4.3 and 13.5 K and, while isothermal induction times between 0 and 15,000 s were observed, the median isothermal induction times for the distributions ranged from 100 to 4000 s. A hyperbolic relationship between median induction time and subcooling was used to correlate the data. A graphical interpretation is presented that relates the two types of data that can be acquired by using the HP‐ALTA in one of two modes to study hydrate formation: induction time distributions at constant subcooling and formation temperature distributions observed during linear cooling ramps. The equivalence of these two modes provides a robust method for studying the variation of formation phenomena in different hydrate systems. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2640–2646, 2013     

相变浆液中甲烷水合物的生成过程强化

利用相变材料（PCM）正十四烷的固液相变过程,吸收甲烷水合释放的热量,实现了直接换热强化水合过程的目的。正十四烷与水混合制成相变乳液（PCE）,经冷却后形成浆液。在半间歇水合器中,测定并计算了甲烷水合物在此浆液中的收率和生成速率。为了提高计算的准确性,设计了一套PVT装置,通过减压法实验测定了低温条件下甲烷在正十四烷中的溶解度。实验结果表明：低温条件下,甲烷在正十四烷中的溶解度与压力基本呈线性关系;相比于间接传热方式下的水合过程,相变浆液中甲烷水合物收率及生成速率得到了有效提升。     

Initial thickness measurements and insights into crystal growth of methane hydrate film

The initial thickness of methane hydrate film was directly measured by suspending a single methane bubble in water at 274.0, 276.0, and 278.0 K. The results show that the initial hydrate film thickness decreases from tens of micrometers to about 10 µm with the subcooling increased from 0.5 K to about 3 K. When subcooling is higher than 1.0 K, all initial film thickness data measured under different temperatures vary inversely with the subcooling. Notable three‐dimensional growths of hydrate crystals of different sizes and shapes at film front and emergence of new crystal were clearly observed at lower subcooling that resulting in the rougher surface of hydrate film and uncertainty of initial thickness measurement under lower subcooling. The hydrate film growth was dominated by film growth in thickness, not by lateral growth at low subcooling. The growth in thickness of hydrate shell covering one whole bubble surface was also investigated. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2145–2154, 2013     

Solubilities of solid n‐alkanes in methane: Data analysis and models assessment

This article reviews the results of experiments underway since 1950 studying the solid solubility of n‐alkanes (from ethane up to n‐triacontane) in methane and the factors influencing the global phase equilibrium behavior of the related binary mixtures. The methodology used consists of a series of comparisons of data in the composition‐temperature and pressure‐temperature diagrams. The kind of global phase diagram of the binary mixtures of methane referred to in the present article is found to be dependent of the ratio between the triple‐point temperature of the generic n‐alkane and the critical‐point temperature of methane. The Peng‐Robinson (1976), Predictive Soave‐Redlich‐Kwong, and Predictive Peng‐Robinson (1978) equations of state have been applied and compared with respect to the calculation of bivariant, univariant, and invariant equilibrium data involving solid n‐alkanes in binary mixture with methane. The fugacities of the solid n‐alkanes have been calculated by means of the so‐called classic approach. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2219–2239, 2018     

An investigation of heat transfer effects in isothermal crystallization studies of low‐density polyethylene

Isothermal crystallization kinetics of low‐density polyethylene (LDPE) were measured from 96°C‐103°C using a power‐compensating differential scanning calorimetry (DSC). Crystallization kinetics were measured using different sample thicknesses and on samples compounded with nickel, a filler with high thermal conductivity. For the unfilled material, sample thickness and temperature had a significant effect on the rate of crystallization as measured by the Avrami rate constant K, but had no effect on the nucleation mechanism and dimensionality of growth, as measured by the Avrami constant n. The crystallization growth rate as expressed by K^1/n scaled approximately with the thickness of the sample. For the filled material, K was much higher and independent of nickel content, suggesting a limiting growth rate for polyethylene at a given temperature in this equipment. The dependence of crystallization rale on sample thickness indicates that barriers to heat transfer can be important. This work shows that for most crystallization rates, thermal conductivity, rather than interfacial resistance between sample and pan, limits heat transfer. Even though thermal conductivity typically dominates heat‐transfer resistance, sample‐pan thermal contact is still important, and some guidelines are given to determine whether good contact is being made.     

Kinetic simulation of methane hydrate formation and dissociation in porous media

The vast amount of hydrocarbon gas deposited in the earth's crust as gas hydrates has significant implications for future energy supply and global climate. A 3-D simulator for methane hydrate formation and dissociation in porous media is developed for designing and interpreting laboratory and field hydrate experiments. Four components (hydrate, methane, water and salt) and five phases (hydrate, gas, aqueous-phase, ice and salt precipitate) are considered in the simulator. The intrinsic kinetics of hydrate formation or dissociation is considered using the Kim-Bishnoi model. Water freezing and ice melting are tracked with primary variable switch method (PVSM) by assuming equilibrium phase transition. Mass transport, including two-phase flow and molecular diffusions, and heat transfer involved in formation or dissociation of hydrates are included in the governing equations, which are discretized with finite volume difference method and are solved in a fully implicit manner. The developed simulator is used here to study the formation and the dissociation of hydrates in laboratory-scale core samples. In hydrate formation from the system of gas and ice (G+I) and in hydrate dissociation systems where ice appears, the equilibrium between aqueous-phase and ice (A-I) is found to have a “blocking” effect on heat transfer when salt is absent from the system. Increase of initial temperature (at constant outlet pressure), introduction of salt component into the system, decrease of outlet pressure, and increase of boundary heat transfer coefficient can lead to faster hydrate dissociation.     

Migration of a single gas bubble in water during the formation of stable gas-hydrate crust on its surface

A theoretical model of gas-hydrate formation during the migration of the methane bubble in water under thermobaric conditions of hydrate stability has been considered. Numeric solutions were obtained and analyzed for two limiting cases when the rate of formation of the hydrate crust on bubble surface is constrained by the intensity of heat removal, which is released during hydrate-formation process by the surrounding water or the diffusive resistance of gas hydrate crust against the transfer of hydrate-forming components. A comparative analysis of the numeric results with the experimental data showed that the diffusive transfer of hydrate-forming components through the crust most adequately described the process of hydrate-particle growth that was observed in experiments during the ascent of methane particles in seawater. The conditions of the best agreement between the theoretical and experimental data on changing of radius of gas-hydrate particle allowed numeric estimates to be obtained for values of the reduced coefficient of gas and water diffusion through the hydrate crust.